Wear-resistant antibacterial elastic plastic floor and preparation method thereof

Abstract

The application discloses a wear-resistant and antibacterial elastic plastic floor and a preparation method thereof, and relates to the technical field of polypropylene. The wear-resistant and antibacterial elastic plastic floor comprises the following raw materials in mass fractions: 70-80 parts of polypropylene masterbatch, 15-35 parts of modified montmorillonite, 10-15 parts of an elastomer toughening agent, 3-5 parts of a compatilizer, 0.1-1 part of an antioxidant and 1-3 parts of a lubricant. The elastomer toughening agent comprises styrene elastomer and propylene-based elastomer at a mass ratio of 1:3-4. The application solves the problem that the styrene elastomer and the propylene-based elastomer have poor compatibility and general toughening effect when used as the elastomer toughening agent, and not only reduces the use of the styrene elastomer with high cost, but also realizes the synergistic promotion of excellent toughness, antibacterial type and anti-aging under a low elastomer addition amount.

Description

Technical Field

[0001] This invention relates to the field of polypropylene technology, specifically to a wear-resistant, antibacterial, and elastic plastic flooring and its preparation method. Background Technology

[0002] Plastic flooring is widely used in commercial and residential decoration due to its advantages such as lightweight, waterproofing, and easy installation. Polypropylene, as a common base resin, is an ideal choice due to its low cost, good wear resistance, and beneficial chemical resistance. To further improve foot comfort and impact resistance, styrene-based elastomers are often added to the PP matrix as toughening agents, or maleic anhydride-grafted polypropylene is commonly used as a modifier to increase toughness, both of which improve the user experience of polypropylene-based plastic flooring to some extent. However, styrene-based elastomers often require complete hydrogenation before being used in polypropylene to achieve excellent anti-aging effects, resulting in higher costs and poor interfacial properties. Maleic anhydride-grafted polypropylene offers limited performance improvements. Furthermore, with the increasing demand for healthy living environments, new requirements have been placed on flooring materials that can achieve antibacterial functions.

[0003] In summary, solving the above problems and providing a wear-resistant, antibacterial, and elastic plastic flooring and its preparation method is of great significance. Summary of the Invention

[0004] The purpose of this invention is to provide a wear-resistant, antibacterial, and elastic plastic flooring and its preparation method, so as to solve the problems mentioned in the background art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A wear-resistant and antibacterial elastic plastic flooring comprises the following raw materials: by weight: 70-80 parts polypropylene masterbatch, 15-35 parts modified montmorillonite, 10-15 parts elastomer toughening agent, 3-5 parts compatibilizer, 0.1-1 parts antioxidant, and 1-3 parts lubricant. The elastomer toughening agent comprises styrene elastomer and propylene-based elastomer in a mass ratio of 1:3 to 4.

[0006] Preferred method for preparing compatibilizer includes the following steps: (1) After irradiating polypropylene masterbatch, stir it with benzoyl peroxide, sodium dodecyl sulfonate and calcium hydroxyphosphate, add styrene and deionized water, stir and react at 95~98℃ for 6~8h, filter, dry and purify to obtain polystyrene grafted polypropylene (PPGPS). (2) Polystyrene-grafted polypropylene (PPGPS) was added to a solvent and stirred for 1-2 hours. 6-bromohexanoyl chloride and aluminum chloride were added and stirred at 25-30°C for 4-8 hours. The mixture was washed with methanol and dried to obtain PPGPS-CO-Br. (3) PPGPS-CO-Br and iodine were added to dimethyl sulfoxide and mixed evenly. The mixture was refluxed and stirred at 60~65℃ for 18~24h. The mixture was washed with methanol and dried to obtain PPGPS-CO-OH-Br. (4) Add PPGPS-CO-OH-Br and trimethylamine to the solvent and stir at 25~30℃ for 24~48h to obtain a compatibilizer.

[0007] Preferably, the polystyrene-grafted polypropylene comprises the following raw materials, by weight: 5-8 parts polypropylene masterbatch, 0.1-0.2 parts benzoyl peroxide, 0.5-2 parts sodium dodecyl sulfonate, 1-5 parts calcium hydroxyphosphate, 8-10 parts styrene, and 90-100 parts deionized water; The PPGPS-CO-Br comprises the following raw materials, by mass parts: 14-16 parts polystyrene-grafted polypropylene, 7-8 parts 6-bromohexanoyl chloride, and 2-3 parts aluminum chloride. The PPGPS-CO-OH-Br comprises the following raw materials, by mass parts: 20-22 parts PPGPS-CO-Br, 6-7 parts elemental iodine, and 100 parts dimethyl sulfoxide; The compatibilizer comprises the following raw materials, by mass: 20-25 parts PPGPS-CO-OH-Br and 5-10 parts trimethylamine.

[0008] Preferably, during the irradiation treatment, the thickness of the polypropylene masterbatch is 0.6~0.8cm, the irradiation dose is 10~12kGy, and the irradiation rate is 3.5~5m / min.

[0009] Preferred method for preparing modified montmorillonite includes the following steps: (1) 1-chloro-6-phenylhexane and trimethylamine are added to dichloromethane and mixed evenly, stirred and reacted at 25-30°C for 12-24 hours, purified, and quaternary ammonium salt phenylhexane is obtained. (2) Disperse montmorillonite in deionized water by ultrasonication, add quaternary ammonium salt phenylhexane, stir and react at 60~65℃ for 3~4h, filter, wash, and dry at 70~80℃ to obtain modified montmorillonite.

[0010] Preferably, the raw materials for the quaternary ammonium phenylhexane include 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.6~1; The modified montmorillonite raw materials include montmorillonite and quaternary ammonium salt phenylhexane in a mass ratio of 1:0.28~0.35.

[0011] A preferred method for preparing a wear-resistant and antibacterial elastic plastic flooring includes the following steps: mixing polypropylene masterbatch, modified montmorillonite, elastomer toughening agent, compatibilizer, antioxidant, and lubricant, followed by melt extrusion, sheeting, and cooling to obtain the wear-resistant and antibacterial elastic plastic flooring.

[0012] Preferably, during the melt extrusion process, the temperatures of each zone of the twin-screw extruder are 160~180℃, 180~190℃, 190~200℃, 200~210℃, 210~215℃, and 200~210℃ respectively.

[0013] Preferably, during the tableting process, the temperature is 180~200℃, the preheating time is 10~20min, the pressure is 5~10MPa, and the compression molding time is 5~15min.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The present invention solves the problem of poor compatibility and general toughening effect when styrene elastomers and propylene elastomers are used as elastomer toughening agents by preparing a compatibilizer containing quaternary ammonium groups and α-hydroxy ketones and adding the prepared modified montmorillonite. Moreover, the present invention not only reduces the use of high-cost styrene elastomers, but also achieves excellent synergistic improvement in toughness, antibacterial properties and anti-aging properties with low elastomer addition.

[0015] The compatibilizer is prepared by irradiating polypropylene masterbatch, followed by suspension polymerization in water using benzoyl peroxide as an initiator, sodium dodecyl sulfonate as an emulsifier, and calcium hydroxyphosphate as a dispersant, with styrene as the grafting monomer, to obtain polystyrene-grafted polypropylene (PPGPS). Further, by introducing α-methylene ketones with bromine end groups onto the benzene ring introduced in PPGPS under the catalysis of Lewis acid catalyst aluminum chloride, PPGPS-CO-Br is obtained. Then, using iodine as a catalyst and dimethyl sulfoxide as an oxidant and solvent, an α-hydroxy ketone structure is generated without affecting the bromine atom. Finally, trimethylamine is used as a nucleophile to react with bromine to form a quaternary ammonium salt, yielding the compatibilizer.

[0016] The compatibilizer in this application has a basic structure of polystyrene-grafted polypropylene, which shares a similar structure with both styrene and propylene-based elastomers, thereby promoting uniform dispersion of the added elastomer and enhancing toughness. By introducing an α-hydroxy ketone structure, hydrogen bonds can be formed between the components. The introduced quaternary ammonium salt has strong electrostatic properties, allowing the compatibilizer to form a cross-linked network in the matrix after addition, maintaining the material's strength. Furthermore, the α-hydroxy ketone possesses excellent antibacterial properties and can synergistically enhance the antibacterial effect with the quaternary ammonium salt. However, α-hydroxy ketones generate free radicals under ultraviolet light. Excessive introduction can lead to a sharp decline in the material's anti-aging properties. Since styrene elastomers still contain a certain amount of double bonds, they are preferentially attacked by the free radicals generated by the α-hydroxy ketone, thus forming cross-linking points. This compensates for the strength decrease caused by molecular chain breakage due to ultraviolet light exposure, improving the aging resistance.

[0017] The modified montmorillonite is prepared by reacting trimethylamine as a nucleophile with chlorine in 1-chloro-6-phenylhexane to generate a quaternary ammonium salt, which is then further prepared by ion exchange intercalation between montmorillonite layers. The modified montmorillonite provides basic strength and protection to the matrix. The introduction of similar benzene rings and alkyl segments through modification improves its dispersibility in the matrix and allows it to act as a second compatibilizer to promote structural stability, maintaining excellent anti-aging, strength, toughness, and antibacterial properties. Detailed Implementation

[0018] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] It should be noted that the following quantities are by weight. There are no special restrictions on the purchasers of any of the raw materials involved in this invention. Exemplary examples include: polypropylene masterbatch, grade A1900; benzoyl peroxide CAS number: 94-36-0; sodium dodecyl sulfonate CAS number: 2386-53-0; calcium hydroxyphosphate CAS number: 1306-06-5; styrene CAS number: 100-42-5; 6-bromohexanoyl chloride CAS number: 22809-37-6; trimethylamine CAS number: 75-50-3; 1-chloro-6-phenylhexane CAS number: 71434-68-9; montmorillonite, grade G105, with a particle size of 16~22μm and an ion exchange capacity of 145mmol / 100g.

[0020] In the following examples, parts refer to parts by weight, and all raw materials mentioned above and others not mentioned are commercially available.

[0021] Among them, the grade of styrene elastomer is 6153; the model of propylene elastomer is CA10A; the antioxidant is antioxidant 1010; and the lubricant is calcium stearate.

[0022] Example 1: A method for preparing a wear-resistant, antibacterial, and elastic plastic flooring, comprising the following steps: Step 1: Preparation of compatibilizer: (1) After irradiating 6 parts of polypropylene masterbatch under the following process conditions: thickness of 0.6 cm, irradiation amount of 10 kGy, irradiation rate of 4 m / min, it was mixed with 0.15 parts of benzoyl peroxide, 1 part of sodium dodecyl sulfonate, and 4 parts of calcium hydroxyphosphate. 9 parts of styrene and 100 parts of deionized water were added, and the mixture was stirred at 96 °C for 7 h. After filtration, drying, and purification, polystyrene-grafted polypropylene (PPGPS) was obtained. (2) 15 parts of polystyrene-grafted polypropylene (PPGPS) were added to 200 parts of dichloromethane and stirred for 1 h. 7.5 parts of 6-bromohexanoyl chloride and 5.5 parts of aluminum chloride were added, and the mixture was stirred at 25 °C for 6 h. After washing with methanol and drying, PPGPS-CO-Br was obtained. (3) Add 21 parts of PPGPS-CO-Br and 6.5 parts of iodine to 100 parts of dimethyl sulfoxide and mix evenly. Reflux and stir at 60°C for 20 h. Wash with methanol and dry to obtain PPGPS-CO-OH-Br; (4) Add 24 parts of PPGPS-CO-OH-Br and 8 parts of trimethylamine to 100 parts of dichloromethane and stir and react at 25°C for 32 h to obtain a compatibilizer; Step 2: Preparation of modified montmorillonite: (1) 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.8 were added to dichloromethane and mixed evenly. The mixture was stirred at 25°C for 24 h and purified to obtain quaternary ammonium phenylhexane. (2) Montmorillonite was ultrasonically dispersed in deionized water and quaternary ammonium phenylhexane in a mass ratio of 1:0.32 was added. The mixture was stirred at 65°C for 3 h, filtered, washed, and dried at 75°C to obtain modified montmorillonite. Step 3: Preparation of wear-resistant and antibacterial elastic plastic flooring: Mix 75 parts of polypropylene masterbatch, 20 parts of modified montmorillonite, 12 parts of elastomer toughening agent (styrene elastomer and propylene-based elastomer in a mass ratio of 1:3.5), 4 parts of compatibilizer, 0.5 parts of antioxidant, and 2 parts of lubricant, then add the mixture to a twin-screw extruder. Set the temperatures of each zone of the twin-screw extruder to 165℃, 185℃, 195℃, 205℃, 215℃, and 210℃ respectively. Melt and mix the mixture, then extrude it into a mold. After preheating at 185℃ for 15 minutes, compress it at 10MPa for 10 minutes and allow it to cool naturally to obtain wear-resistant and antibacterial elastic plastic flooring.

[0023] Example 2: A method for preparing a wear-resistant, antibacterial, and elastic plastic flooring, comprising the following steps: Step 1: Preparation of compatibilizer: (1) After irradiating 6 parts of polypropylene masterbatch under the following process conditions: thickness of 0.6 cm, irradiation amount of 10 kGy, irradiation rate of 4 m / min, it was mixed with 0.15 parts of benzoyl peroxide, 1 part of sodium dodecyl sulfonate, and 4 parts of calcium hydroxyphosphate. 9 parts of styrene and 100 parts of deionized water were added, and the mixture was stirred at 96 °C for 7 h. After filtration, drying, and purification, polystyrene-grafted polypropylene (PPGPS) was obtained. (2) 15 parts of polystyrene-grafted polypropylene (PPGPS) were added to 200 parts of dichloromethane and stirred for 1 h. 7.5 parts of 6-bromohexanoyl chloride and 5.5 parts of aluminum chloride were added, and the mixture was stirred at 25 °C for 6 h. After washing with methanol and drying, PPGPS-CO-Br was obtained. (3) Add 21 parts of PPGPS-CO-Br and 6.5 parts of iodine to 100 parts of dimethyl sulfoxide and mix evenly. Reflux and stir at 60°C for 20 h. Wash with methanol and dry to obtain PPGPS-CO-OH-Br; (4) Add 24 parts of PPGPS-CO-OH-Br and 8 parts of trimethylamine to 100 parts of dichloromethane and stir and react at 25°C for 32 h to obtain a compatibilizer; Step 2: Preparation of modified montmorillonite: (1) 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.8 were added to dichloromethane and mixed evenly. The mixture was stirred at 25°C for 24 h and purified to obtain quaternary ammonium phenylhexane. (2) Montmorillonite was ultrasonically dispersed in deionized water and quaternary ammonium phenylhexane in a mass ratio of 1:0.32 was added. The mixture was stirred at 65°C for 3 h, filtered, washed, and dried at 75°C to obtain modified montmorillonite. Step 3: Preparation of wear-resistant and antibacterial elastic plastic flooring: Mix 70 parts of polypropylene masterbatch, 15 parts of modified montmorillonite, 10 parts of elastomer toughening agent (styrene elastomer and propylene-based elastomer in a mass ratio of 1:3), 5 parts of compatibilizer, 0.1 parts of antioxidant, and 2 parts of lubricant, then add the mixture to a twin-screw extruder. Set the temperatures of each zone of the twin-screw extruder to 165℃, 185℃, 195℃, 205℃, 215℃, and 210℃ respectively. Melt and mix the mixture, then extrude it into a mold. After preheating at 185℃ for 15 minutes, press-molde at 10MPa for 10 minutes, and allow it to cool naturally to obtain wear-resistant and antibacterial elastic plastic flooring.

[0024] Example 3: A method for preparing a wear-resistant, antibacterial, and elastic plastic flooring, comprising the following steps: Step 1: Preparation of compatibilizer: (1) After irradiating 6 parts of polypropylene masterbatch under the following process conditions: thickness of 0.6 cm, irradiation amount of 10 kGy, irradiation rate of 4 m / min, it was mixed with 0.15 parts of benzoyl peroxide, 1 part of sodium dodecyl sulfonate, and 4 parts of calcium hydroxyphosphate. 9 parts of styrene and 100 parts of deionized water were added, and the mixture was stirred at 96 °C for 7 h. After filtration, drying, and purification, polystyrene-grafted polypropylene (PPGPS) was obtained. (2) 15 parts of polystyrene-grafted polypropylene (PPGPS) were added to 200 parts of dichloromethane and stirred for 1 h. 7.5 parts of 6-bromohexanoyl chloride and 5.5 parts of aluminum chloride were added, and the mixture was stirred at 25 °C for 6 h. After washing with methanol and drying, PPGPS-CO-Br was obtained. (3) Add 21 parts of PPGPS-CO-Br and 6.5 parts of iodine to 100 parts of dimethyl sulfoxide and mix evenly. Reflux and stir at 60°C for 20 h. Wash with methanol and dry to obtain PPGPS-CO-OH-Br; (4) Add 24 parts of PPGPS-CO-OH-Br and 8 parts of trimethylamine to 100 parts of dichloromethane and stir and react at 25°C for 32 h to obtain a compatibilizer; Step 2: Preparation of modified montmorillonite: (1) 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.8 were added to dichloromethane and mixed evenly. The mixture was stirred at 25°C for 24 h and purified to obtain quaternary ammonium phenylhexane. (2) Montmorillonite was ultrasonically dispersed in deionized water and quaternary ammonium phenylhexane in a mass ratio of 1:0.32 was added. The mixture was stirred at 65°C for 3 h, filtered, washed, and dried at 75°C to obtain modified montmorillonite. Step 3: Preparation of wear-resistant and antibacterial elastic plastic flooring: Mix 80 parts of polypropylene masterbatch, 35 parts of modified montmorillonite, 15 parts of elastomer toughening agent (styrene elastomer and propylene-based elastomer in a mass ratio of 1:4), 5 parts of compatibilizer, 1 part of antioxidant, and 2 parts of lubricant, then add the mixture to a twin-screw extruder. Set the temperatures of each zone of the twin-screw extruder to 165℃, 185℃, 195℃, 205℃, 215℃, and 210℃ respectively. Melt and mix the mixture, then extrude it into a mold. After preheating at 185℃ for 15 minutes, compress it at 10MPa for 10 minutes and allow it to cool naturally to obtain wear-resistant and antibacterial elastic plastic flooring.

[0025] Comparative Example 1: Based on Example 1, without adding a compatibilizer, and with the remaining processes unchanged, as follows: Step 1: Preparation of modified montmorillonite: (1) 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.8 were added to dichloromethane and mixed evenly. The mixture was stirred at 25°C for 24 h and purified to obtain quaternary ammonium phenylhexane. (2) Montmorillonite was ultrasonically dispersed in deionized water and quaternary ammonium phenylhexane in a mass ratio of 1:0.32 was added. The mixture was stirred at 65°C for 3 h, filtered, washed, and dried at 75°C to obtain modified montmorillonite. Step 2: Preparation of wear-resistant and antibacterial elastic plastic flooring: 79 parts of polypropylene masterbatch, 20 parts of modified montmorillonite, 12 parts of elastomer toughening agent (styrene elastomer and propylene-based elastomer in a mass ratio of 1:3.5), 0.5 parts of antioxidant, and 2 parts of lubricant are mixed and added to a twin-screw extruder. The temperatures of each zone of the twin-screw extruder are set to 165℃, 185℃, 195℃, 205℃, 215℃, and 210℃ respectively. The mixture is melted and extruded into a mold. After preheating at 185℃ for 15 minutes, it is press-molded at 10MPa for 10 minutes and then naturally cooled to obtain wear-resistant and antibacterial elastic plastic flooring.

[0026] Comparative Example 2: Based on Example 1, the amount of compatibilizer added was increased, while the rest of the process remained unchanged, as follows: Step 1: Preparation of compatibilizer: (1) After irradiating 6 parts of polypropylene masterbatch under the following process conditions: thickness of 0.6 cm, irradiation amount of 10 kGy, irradiation rate of 4 m / min, it was mixed with 0.15 parts of benzoyl peroxide, 1 part of sodium dodecyl sulfonate, and 4 parts of calcium hydroxyphosphate. 9 parts of styrene and 100 parts of deionized water were added, and the mixture was stirred at 96 °C for 7 h. After filtration, drying, and purification, polystyrene-grafted polypropylene (PPGPS) was obtained. (2) 15 parts of polystyrene-grafted polypropylene (PPGPS) were added to 200 parts of dichloromethane and stirred for 1 h. 7.5 parts of 6-bromohexanoyl chloride and 5.5 parts of aluminum chloride were added, and the mixture was stirred at 25 °C for 6 h. After washing with methanol and drying, PPGPS-CO-Br was obtained. (3) Add 21 parts of PPGPS-CO-Br and 6.5 parts of iodine to 100 parts of dimethyl sulfoxide and mix evenly. Reflux and stir at 60°C for 20 h. Wash with methanol and dry to obtain PPGPS-CO-OH-Br; (4) Add 24 parts of PPGPS-CO-OH-Br and 8 parts of trimethylamine to 100 parts of dichloromethane and stir and react at 25°C for 32 h to obtain a compatibilizer; Step 2: Preparation of modified montmorillonite: (1) 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.8 were added to dichloromethane and mixed evenly. The mixture was stirred at 25°C for 24 h and purified to obtain quaternary ammonium phenylhexane. (2) Montmorillonite was ultrasonically dispersed in deionized water and quaternary ammonium phenylhexane in a mass ratio of 1:0.32 was added. The mixture was stirred at 65°C for 3 h, filtered, washed, and dried at 75°C to obtain modified montmorillonite. Step 3: Preparation of wear-resistant and antibacterial elastic plastic flooring: Mix 67 parts of polypropylene masterbatch, 20 parts of modified montmorillonite, 12 parts of elastomer toughening agent (styrene elastomer and propylene-based elastomer in a mass ratio of 1:3.5), 12 parts of compatibilizer, 0.5 parts of antioxidant, and 2 parts of lubricant, then add the mixture to a twin-screw extruder. Set the temperatures of each zone of the twin-screw extruder to 165℃, 185℃, 195℃, 205℃, 215℃, and 210℃ respectively. Melt and mix the mixture, then extrude it into a mold. After preheating at 185℃ for 15 minutes, press-molde at 10MPa for 10 minutes, and allow it to cool naturally to obtain wear-resistant and antibacterial elastic plastic flooring.

[0027] Comparative Example 3: Based on Example 1, the mass ratio of styrene elastomer and propylene-based elastomer was changed, while the other processes remained unchanged, as follows: Step 1: Preparation of compatibilizer: (1) After irradiating 6 parts of polypropylene masterbatch under the following process conditions: thickness of 0.6 cm, irradiation amount of 10 kGy, irradiation rate of 4 m / min, it was mixed with 0.15 parts of benzoyl peroxide, 1 part of sodium dodecyl sulfonate, and 4 parts of calcium hydroxyphosphate. 9 parts of styrene and 100 parts of deionized water were added, and the mixture was stirred at 96 °C for 7 h. After filtration, drying, and purification, polystyrene-grafted polypropylene (PPGPS) was obtained. (2) 15 parts of polystyrene-grafted polypropylene (PPGPS) were added to 200 parts of dichloromethane and stirred for 1 h. 7.5 parts of 6-bromohexanoyl chloride and 5.5 parts of aluminum chloride were added, and the mixture was stirred at 25 °C for 6 h. After washing with methanol and drying, PPGPS-CO-Br was obtained. (3) Add 21 parts of PPGPS-CO-Br and 6.5 parts of iodine to 100 parts of dimethyl sulfoxide and mix evenly. Reflux and stir at 60°C for 20 h. Wash with methanol and dry to obtain PPGPS-CO-OH-Br; (4) Add 24 parts of PPGPS-CO-OH-Br and 8 parts of trimethylamine to 100 parts of dichloromethane and stir and react at 25°C for 32 h to obtain a compatibilizer; Step 2: Preparation of modified montmorillonite: (1) 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.8 were added to dichloromethane and mixed evenly. The mixture was stirred at 25°C for 24 h and purified to obtain quaternary ammonium phenylhexane. (2) Montmorillonite was ultrasonically dispersed in deionized water and quaternary ammonium phenylhexane in a mass ratio of 1:0.32 was added. The mixture was stirred at 65°C for 3 h, filtered, washed, and dried at 75°C to obtain modified montmorillonite. Step 3: Preparation of wear-resistant and antibacterial elastic plastic flooring: Mix 75 parts of polypropylene masterbatch, 20 parts of modified montmorillonite, 12 parts of elastomer toughening agent (styrene elastomer and propylene elastomer in a mass ratio of 3.5:1), 4 parts of compatibilizer, 0.5 parts of antioxidant, and 2 parts of lubricant, then add the mixture to a twin-screw extruder. Set the temperatures of each zone of the twin-screw extruder to 165℃, 185℃, 195℃, 205℃, 215℃, and 210℃ respectively. Melt and mix the mixture, then extrude it into a mold. After preheating at 185℃ for 15 minutes, compress it at 10MPa for 10 minutes and allow it to cool naturally to obtain wear-resistant and antibacterial elastic plastic flooring.

[0028] Comparative Example 4: Based on Example 1, 1-chloro-6-phenylhexanone was replaced with 6-chloro-1-phenyl-1-hexanone in the montmorillonite modification process, while the rest of the process remained unchanged, as follows: Step 1: Preparation of compatibilizer: (1) After irradiating 6 parts of polypropylene masterbatch under the following process conditions: thickness of 0.6 cm, irradiation amount of 10 kGy, irradiation rate of 4 m / min, it was mixed with 0.15 parts of benzoyl peroxide, 1 part of sodium dodecyl sulfonate, and 4 parts of calcium hydroxyphosphate. 9 parts of styrene and 100 parts of deionized water were added, and the mixture was stirred at 96 °C for 7 h. After filtration, drying, and purification, polystyrene-grafted polypropylene (PPGPS) was obtained. (2) 15 parts of polystyrene-grafted polypropylene (PPGPS) were added to 200 parts of dichloromethane and stirred for 1 h. 7.5 parts of 6-bromohexanoyl chloride and 5.5 parts of aluminum chloride were added, and the mixture was stirred at 25 °C for 6 h. After washing with methanol and drying, PPGPS-CO-Br was obtained. (3) Add 21 parts of PPGPS-CO-Br and 6.5 parts of iodine to 100 parts of dimethyl sulfoxide and mix evenly. Reflux and stir at 60°C for 20 h. Wash with methanol and dry to obtain PPGPS-CO-OH-Br; (4) Add 24 parts of PPGPS-CO-OH-Br and 8 parts of trimethylamine to 100 parts of dichloromethane and stir and react at 25°C for 32 h to obtain a compatibilizer; Step 2: Preparation of modified montmorillonite: (1) 6-chloro-1-phenyl-1-hexanone and trimethylamine in a mass ratio of 1:0.8 were added to dichloromethane and mixed evenly. The mixture was stirred at 25°C for 24 h and purified to obtain quaternary ammonium salt phenylhexanone; (2) Montmorillonite was ultrasonically dispersed in deionized water, and quaternary ammonium salt phenylhexanone in a mass ratio of 1:0.32 was added. The mixture was stirred at 65°C for 3 h, filtered, washed, and dried at 75°C to obtain modified montmorillonite; Step 3: Preparation of wear-resistant and antibacterial elastic plastic flooring: Mix 75 parts of polypropylene masterbatch, 20 parts of modified montmorillonite, 12 parts of elastomer toughening agent (styrene elastomer and propylene-based elastomer in a mass ratio of 1:3.5), 4 parts of compatibilizer, 0.5 parts of antioxidant, and 2 parts of lubricant, then add the mixture to a twin-screw extruder. Set the temperatures of each zone of the twin-screw extruder to 165℃, 185℃, 195℃, 205℃, 215℃, and 210℃ respectively. Melt and mix the mixture, then extrude it into a mold. After preheating at 185℃ for 15 minutes, compress it at 10MPa for 10 minutes and allow it to cool naturally to obtain wear-resistant and antibacterial elastic plastic flooring.

[0029] Performance testing: The test data for each embodiment and comparative example are shown in the table below: Example 1 29.2 94.3 35.0 99.6 Example 2 27.5 92.8 37.2 99.5 Example 3 28.3 93.5 36.1 99.5 Comparative Example 1 21.5 88.5 22.8 85.2 Comparative Example 2 25.2 65.0 33.5 99.7 Comparative Example 3 26.8 89.2 25.3 98.9 Comparative Example 4 24.7 63.5 29.6 97.5 Conclusions: In Comparative Example 1, without the addition of a compatibilizer, the toughening agent composed of styrene elastomer and propylene-based elastomer showed poor compatibility with the matrix, resulting in a mediocre toughening effect, decreased impact strength, and reduced yield tensile strength. In Comparative Example 2, increasing the amount of compatibilizer led to the generation of a large number of free radicals in the α-hydroxy ketone structure of the matrix, which damaged the original structure and significantly reduced the strength retention rate after aging. In Comparative Example 3, changing the mass ratio of styrene elastomer to propylene-based elastomer revealed a decrease in overall performance, indicating that the compatibilizer provided in this application reduces the use of styrene elastomer while maintaining excellent performance. In Comparative Example 4, 6-chloro-1-phenyl-1-hexanone was used to replace 1-chloro-6-phenylhexane during the montmorillonite modification process. Although the structure was more similar to the compatibilizer, the anti-aging performance decreased significantly. This is because the ketone group connecting the benzene ring acts as a photosensitizer under ultraviolet light, generating additional free radicals, leading to deterioration of material performance.

[0030] In summary, this invention solves the problems of poor compatibility and mediocre toughening effect when styrene elastomers and propylene elastomers are used as elastomer toughening agents by preparing a compatibilizer containing quaternary ammonium groups and α-hydroxy ketones and adding the prepared modified montmorillonite. Moreover, this invention not only reduces the use of costly styrene elastomers, but also achieves excellent synergistic improvement in toughness, antibacterial properties, and anti-aging properties with low elastomer addition.

[0031] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a wear-resistant, antibacterial, elastic plastic floor, characterized in that: Includes the following steps: Mix 70-80 parts of polypropylene masterbatch, 15-35 parts of modified montmorillonite, 10-15 parts of elastomer toughening agent, 3-5 parts of compatibilizer, 0.1-1 parts of antioxidant, and 1-3 parts of lubricant, then melt-extrude, press into sheets, and cool to obtain wear-resistant and antibacterial elastic plastic flooring. The elastomer toughening agent comprises styrene elastomer and propylene-based elastomer in a mass ratio of 1:3 to 4. The preparation method of the compatibilizer includes the following steps: (1) After irradiating polypropylene masterbatch, stir it with benzoyl peroxide, sodium dodecyl sulfonate and calcium hydroxyphosphate, add styrene and deionized water, stir and react at 95~98℃ for 6~8h, filter, dry and purify to obtain polystyrene-grafted polypropylene; (2) Add polystyrene-grafted polypropylene to solvent, stir for 1~2h, add 6-bromohexanoyl chloride and aluminum chloride, stir and react at 25~30℃ for 4~8h, wash with methanol, dry to obtain PPGPS-CO-Br; (3) Add PPGPS-CO-Br and iodine to dimethyl sulfoxide and mix evenly, reflux and stir at 60~65℃ for 18~24h, wash with methanol, dry to obtain PPGPS-CO-OH-Br; (4) Add PPGPS-CO-OH-Br and trimethylamine to solvent, stir and react at 25~30℃ for 24~48h to obtain compatibilizer; The compatibilizer is formed by suspension polymerization of polystyrene-grafted polypropylene after irradiation treatment of polypropylene masterbatch with styrene as the grafting monomer; then, α-methylene ketones with bromine end groups are grafted onto the introduced benzene ring under the catalysis of aluminum chloride to obtain PPGPS-CO-Br. Furthermore, iodine is used as a catalyst, and dimethyl sulfoxide is used as an oxidant and solvent to generate the α-hydroxy ketone structure PPGPS-CO-OH-Br without affecting the bromine atom. Finally, the compatibilizer is obtained by reacting trimethylamine with the bromine at the end groups to form a quaternary ammonium salt.

2. The method for preparing a wear-resistant, antibacterial, elastic plastic flooring according to claim 1, characterized in that: The polystyrene-grafted polypropylene comprises the following raw materials, by weight: 5-8 parts polypropylene masterbatch, 0.1-0.2 parts benzoyl peroxide, 0.5-2 parts sodium dodecyl sulfonate, 1-5 parts calcium hydroxyphosphate, 8-10 parts styrene, and 90-100 parts deionized water; The PPGPS-CO-Br comprises the following raw materials, by mass parts: 14-16 parts polystyrene-grafted polypropylene, 7-8 parts 6-bromohexanoyl chloride, and 2-3 parts aluminum chloride. The PPGPS-CO-OH-Br comprises the following raw materials, by mass parts: 20-22 parts PPGPS-CO-Br, 6-7 parts elemental iodine, and 100 parts dimethyl sulfoxide; The compatibilizer comprises the following raw materials, by mass: 20-25 parts PPGPS-CO-OH-Br and 5-10 parts trimethylamine.

3. The method for preparing a wear-resistant, antibacterial, elastic plastic flooring according to claim 1, characterized in that: During the irradiation process, the thickness of the polypropylene masterbatch is 0.6~0.8cm, the irradiation dose is 10~12kGy, and the irradiation rate is 3.5~5m / min.

4. The method for preparing a wear-resistant, antibacterial, elastic plastic flooring according to claim 1, characterized in that: The preparation method of the modified montmorillonite includes the following steps: (1) 1-chloro-6-phenylhexane and trimethylamine are added to dichloromethane and mixed evenly, stirred and reacted at 25~30℃ for 12~24h, purified, and quaternary ammonium salt phenylhexane is obtained; (2) Disperse montmorillonite in deionized water by ultrasonication, add quaternary ammonium salt phenylhexane, stir and react at 60~65℃ for 3~4h, filter, wash, and dry at 70~80℃ to obtain modified montmorillonite.

5. The method for preparing a wear-resistant, antibacterial, elastic plastic flooring according to claim 4, characterized in that: The raw materials for the quaternary ammonium salt phenylhexane include 1-chloro-6-phenylhexane and trimethylamine in a mass ratio of 1:0.6~1; The modified montmorillonite raw materials include montmorillonite and quaternary ammonium salt phenylhexane in a mass ratio of 1:0.28~0.

35.

6. The method for preparing a wear-resistant, antibacterial, elastic plastic flooring according to claim 1, characterized in that: During the melt extrusion process, the temperatures of each zone of the twin-screw extruder are 160~180℃, 180~190℃, 190~200℃, 200~210℃, 210~215℃, and 200~210℃, respectively.

7. The method for preparing a wear-resistant, antibacterial, elastic plastic flooring according to claim 1, characterized in that: During the tableting process, the temperature is 180~200℃, the preheating time is 10~20min, the pressure is 5~10MPa, and the compression molding time is 5~15min.

8. The plastic flooring prepared by the method for preparing a wear-resistant, antibacterial, elastic plastic flooring according to any one of claims 1 to 7.